Method for making sulfur-containing phthalocyanine dyestuffs



United States Patent 3,378,568 METHOD FDR MAKllNG SULFUR-CQNTA1NHNG PHTHALUCYANINE DYESTUFFS Wilson J. Bryan, .lr., Charlotte, and William S. Griffith,

Mount Holly, N.C., assignors to Martin-Marietta Corporation, a corporation of Maryiand No Drawing. Filed Dec. 20, 1965, Ser. No. 515,192 3 Ciaims. ((11. 266-4145) ABSTRACT 6F THE DISCLOSURE There is disclosed herein a method for making vattable, sulfur-containing dyestuffs of the phthalocyanine series, comprising heating phthalocyanine sulfinates, copper phthalocyanine sulfinates or nickel phthalocyanine sulfinates, in which the sulfinate groups are pendant and are substituents for hydrogen in the arylene nuclei of the phthalocyanines, with X 8 0 or sodium polysulfides, wherein X is Na, K or NH The phthalocyanines may contain in addition pendant thiolsulfonate groups or pendant sulfonate groups. Solubilization of the resulting dye to its leuco form with sodium sulfide, and production of wetfast green dyeings with the dyestuii on cotton fabric is also disclosed.

The present invention relates to dyestuffs, and more particularly to a method for making vattable, sulfur-corn taining dyestuifs of the phthalocyanine series which are soluble in aqueous sodium sulfide.

Generally speaking, the method of the present invention is a process for making vattable, sulfur-containing dyestuffs of the phtnalocyanine ser'es, which comprises heating a sulfinate of the phthalocyanine series selected from the group consisting of phthalocyanine sulfinates, copper phthalocyanine sulfinates and nickel phthalocyanine sulfinates, in which the sulfinate groups are pendant and are substituents for hydrogen in the arylene nuclei of the phthalocyanines, with a member selected from the group consisting of X 8 0 and sodium polysulfides, wherein X is a member selected from the group consisting of Na, K and N11 The suliinates of the phthalocyanine series may also contain pendant thiolsulfonate groups or pendant sulfonate groups in addition to the pendant sulrinate groups.

The dyestuffs of the present invention may be solubilized to their leuco form with aqueous sodium sulfide, and the leuco may be padded onto cotton fabric, dried, and subsequently oxidized to make valuable wet-fast green dyeings.

The method of the present invention has a number of advantages. For example, it is economical in that relatively inexpensive materials may be selected as starting products; Na S O is a preferred reactant and is readily available in quantity as a difficultly disposable Waste product at sulfur dye plants. Further economics and safety result because the reaction may be conducted rapidly in aqueous medium using non-corrosive and stable reactants, without any necessity for expensive solvents or glasslined equilibrium. Moreover, the final product is easily isolated from the other end products. Additional advantages will become apparent from the following detailed description.

The starting sulfinate is a sulfinate of the phthalocyanine series selected from the group consisting of phthalocyanine sulfinates, nickel phthalocyanine sulfinates and copper phthalocyanine sulfinates, in which the sulfinate groups are pendant and are substituents for hydrogen in the arylene nuclei of the phthalocyanines.

The phthalocyanine sulfinates may also contain pend- 3,378,568 Patented Apr. 16, 1968 ant thiolsulfonate or pendant sulfonate groups, which are also substituents for hydrogen in the arylene nuclei of the phthalocyanines, in addition to the pendant sulfinate groups.

Examples of sulfinates of the phthalocyanine series which are suitable for use in the method of the present invention are those disclosed in British patent specification No. 960,643, published June 10, 1964.

However, for reasons of economy it is preferred to use sulfinates of the phthalocyanine series of the formula (S iS-Na) which may be prepared by a process comprising the step of reducing Pc SO CU in aqueous medium at pH 4-10 with an excess of NaSH or Na s, wherein Fe is the radical of phthalocyanine, copper phthalocyanine or nickel phthalocyauine, x is a number from 1.2-2.3, y is a numher from 0.84.3, n is a number from 2-4, and x+y=n.

The phthalocyanine suifinate is preferably dissolved in water, for reasons of economy. However, a suitable organic solvent may be used, but will be more expensive. Suitable organic solvents are those in which the reactants are soluble, which do not react with the reactants, and which do not boil at less than C. under the reaction conditions. If an organic solvent is selected, it is desirable that the solvent be one in which the final product is insoluble, for ease in isolatin the product.

N21 S O K S O (NH S O or a sodium polysulfide is then added to the solution of the phthalocyanine sulfinate. It is suggested that an excess of the thiosulfate compound or the sodium polysulfide be used; by excess it is meant that more than the theoretical amount required to complete the reaction be employed. A suitable range would be about 4-8, and preferably 5, gram molecular weights of the thiosulfate per gram molecular weight of the phthalocyanine sulfinate selected multiplied by the sum of the sulfinate and thiolsulfonate groups per molecule of phthalocyanine; when sodium polysulfideis employed, reduce the above 4-8, and preferably 5, to 1-2, and preferably 1.25. For example, if 1 g.-m.w. of

CuPc

(SOzS-Na)i.1 wherein CuPc is the radical of copper phthnlocyanine, were employed, 1642, and preferably 20, g.m.w. of Na S O would be used; or 4-8, and preferably 5, g.m.w. of a sodium polysulfide could be substituted for the N82S2O3.

It is suggested that the pH of the composition for the reaction be 7]O, as lower pH results in undesirable sulfur precipitation. The composition for the reaction will usually be within this pH range, but if not an alkali or acid binding agent; such as NaOH, Na S, or Na CO can be employed to adjust the pH to the desired range.

The reaction is conducted at an elevated temperature, preferably within the range of about 140-180 C. If water is used as the solvent, about 38-170 p.s.i.g. pressure results when the desired temperature is obtained, and therefore the reaction should be conducted in a sealed pressure vessel. If organic solvents are used, a desirable reaction temperature may be obtained at atmospheric pressure.

The composition is heated until the phthalocyanine suitinate has been converted into the vattable, sulfur-containing dyestuff of the phthalocyanine series. The dyestuffs 0f the present invention are vattable from an aqueous sulfide solution thereof; The length of time during which the composition is heated depends, of course, on the temperature employed. In general, heating may be from about 10 minutes-2 hours. The reaction is substantially complete within a few minutes, but heating may continue for a longer period to insure completion of reaction. Completion of the reaction is indicated by precipitation of the product.

Following completion of the reaction, the product is isolated as solids, for example, the slurry containing the product is cooled 'below 50 C., the product collected in solids form by filtration, and the solids Washed with water at room temperature and dried.

The product may be marketed as solids, or it may be reduced to the leuco form with aqueous N21 S and marketed as a concentrated pre-reduced liquid dye.

It is believed that the product is a phthalocyanine polymer containing disulfide or polysulfide linkages, and may be represented by the formula wherein Fe and X are as above defined; m is the number of S atoms in each polysulfide unit; t is a number from 1 through 4; d is zero or the number of sulfonate groups per Pc; p is the number of non-terminal Pc units; a is l-3 and less than t; and the sum of t-l-d is not greater than 4. It is possible that bridging members, for example S or SO, may be interposed between some or all of the Po and Sm groups or units. However, all of the foregoing belief is theory to which we do not wish to be bound.

The following are illustrative examples for preparing the green phthalocyanine dyes of the present invention.

EXAMPLE 1 An aqueous solution of a water soluble copper phthalocyanine sulfinate of the formula (SO2-N0Jr .1

CuPc

(SOz-S-NtDu wherein CuPc is the radical of copper phthalocyanine, is prepared by slurrying 97 gms. copper phthalocyanine tetra-(3)-sulfonyl chloride with ice and water to 960 ml. volume at 0 C., adjusting the pH to 7 by adding 15% aqueous NaOH at room temperature to the cold mass, adding 3 drops tributyl phosphate anti-foaming agent, adding 77.9 gms. 43% aqueous NaSH solution at room temperature, warming to room temperature over 1 hour, and stirring 3 additional hours.

The resulting solution is transferred to a pressure reaction vessel, and 496 gms. Na S O -H O are added thereto. The resulting solution is heated at 175 180 C. for 1 hour in a sealed vessel, during which the pressure rises to 120150 p.s.i.g. The resulting slurry is cooled to below 50 C., the solids product recovered by filtration, washed with water at room temperature and dried.

EXAMPLE 2 97 gms. copper phthalocyanine tetra-(4)sulfonyl chloride are stirred with ice and water to 600 ml. volume at 0 C., and 3 drops tributyl phosphate are added. The pH is adjusted to 5 by adding aqueous NaOH at room temperature to the cold mass. 69.1 gms. Na s dissolved in 300 ml. water at room temperature, and enough ice to maintain the mass at 0 C. during addition of the Na S, are added. The mass is stirred 12-15 hours while permitting it to warm to room temperature naturally. An aqueous solution of S0 2-Na) 2 .a

CuPc

(S Or-S-Na) l .1

wherein CuPc is the radical of copper phthalocyanine, results.

The pH of the above aqueous solution is adjusted to 7 with HCl or NH OH as required. 474 gms. (NH S O is added thereto, and the resulting solution heated in a sealed vessel for 10 hours at C. The resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature and dried.

EXAMPLE 3 An aqueous solution of is prepared in the same manner as in Example 2 above, except that 96.5 gms. nickel phthalocyanine tetra-(3)- sulfonyl chloride is substituted for the copper phthalocyanine tetra-(4)sulfonyl chloride used in Example 2.

The pH of the above aqueous solution is adjusted to 8 with KOH or HCl as required, 334 gms. K 8 0 11 0 added thereto, and the resulting solution heated in a sealed vessel for 2 hours at 180 C. The resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature, and collected as moist press cake for subsequent conversion with aqueous Na S to a water soluble, concentrated, prereduced, liquid dye.

EXAMPLE 4 An aqueous solution of (SOsah:

(S 0 2SNa) r .1

wherein Z is the radical of phthalocyanine, is prepared in the same manner as disclosed in Example 2 above, except that 90.65 gms. phthalocyanine tetra-(4)-sulfonyl chloride are substituted for the copper phthalocyanine tetra-(4)-sulfonyl chloride used in Example 2.

The pH of the above aqueous solution is adjusted to 9 with NaOH or HCl as required, 35% aqueous Na S added thereto, and the resulting solution heated in a sealed vessel for 30 minutes at 180 C. The resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature and dried.

EXAMPLE 5 84.2 gms. of the dried copper phthalocyanine sulfinic acid having an average of 3.4 s-ulfinic acid groups per molecule is prepared according to Example 4 of British patent specification No. 960,643, published June 10, 1964, powdered, blended with enough Na CO solids so that a 10% aqueous solution thereof would have PH 10, dissolved to a volume of 1,000 ml. with water, 354 gms. K S O -H O is added, and the resulting solution is heated in a sealed vessel 1 hour at 175 C. The resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature and dried.

EXAMPLE 6 83.7 gms. of dried nickel phthalocyanine sulfinic acid having an average of 3.4 sulfinic acid groups per molecule is prepared according to Example 4 of British patent specification No. 960,643, published June 10, 1964, except that 9.65 parts nickel phthalocyanine tetra-(4)-sulfonyl chloride are substituted for the 9.7 parts copper phthalocyanine tetra-(3)-sulfonyl chloride used therein.

The dried nickel phthalocyanine sulfinic acid is powdered, blended with enough Na CO solids so that a 10% aqueous solution thereof would have pH 7, dissolved to 800 ml. volume with water, and 252 gms. (NH S O is added thereto. The resulting solution is heated in a sealed vessel 1 hour at -175 C., and the resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with Water at room temperature, and dried.

EXAMPLE 7 78 gms. dried phthalocyanine sulfinic acid having an average of 3.4 sulfinic acid groups per molecule is prepared according to Example 4 of British patent specification No. 960,643, published June 10, 1964, except that 9.09 parts phthalocyanine tetra-(3)-sulfonyl chloride is substituted for the 9.7 parts copper phthalocyanine tetra- (3)-snlfonyl chloride used therein.

The dried phthalocyanine sulfinic acid is dissolved in water with enough NaOH to give final volume of 1,000 ml. and pH 8; 421 gms. Na S O -5H O is added thereto, and the resulting solution is heated in a sealed vessel for 4 hours at 150 C. The resulting slurry is cooled below 50 C., the solids collected by filtration, washed with water at room temperature and dried.

EXAMPLE 8 83.7 gms. dried nickel phthalocyanine sulfinic acid having an average of 3.4 sulfinic acid groups per molecule is prepared according to Example 6 above.

The dried nickel phthalocyanine sulfinic acid is powdered, blended with enough Na CO solids so that a aqueous solution thereof would have pH 8, dissolved to 700 ml. volume with water, and 134.5 gms. 44% aqueous Na S is added thereto. The resulting solution is heated in a sealed vessel 3 hours at 180 C.; the resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature, and dried.

EXAMPLE 9 An aqueous solution of SOz-Nahx CuPc (SOs-S-Nahs wherein CuPc is the radical of copper phthalocyanine, is prepared by stirring 87.15 gms. copper phthalocyanine tri-(3)-sulfonyl chloride with ice and water to 900 ml. volume at 0 C., and 3 drops tributyl phosphate are added. The pH is adjusted to 7 by adding aqueous NaOH at room temperature to the cold mass. 519 gms. of 43% aqueous NaSH solution at room temperature is added to the cold mass, and the mass is stirred 12-15 hours while being permitted to warm to room temperature naturally.

To the resulting solution is added 152 gms. 25% aqueous Na S and the resulting solution is heated in a sealed vessel 1 hour at 145 C.; the resulting slurry is cooled below 50 C., the solids product collected by filtration, 0

washed with Water at room temperature, and dried.

EXAMPLE 10 This example is the same as Example 9 above, except that 86.7 gms. nickel phthalocyanine tri-(4)-sulfonyl chloride is substituted for the copper phthalocyanine tri-(3)- sulfonyl chloride used in Example 9, and except that 372 gms. Na S O -SH O is substituted for the aqueous Na S used in Example 9.

EXAMPLE 11 This example is the same as Example 9 above, except that 80.1 gms. phthalocyanine tri-(3)-sulfonyl chloride is substituted for the copper phthalocyanine tri-(3)-sulfonyl chloride used in Example 9, and except that 312 gms. K S O -H O is substituted for the aqueous Na S used in Example 9.

EXAMPLE 12 This example is the same as Example 11 above, except that 213 gms. 25% aqueous Na S is substituted for the K S O -I-I O used in Example 11.

EXAMPLE 13 78.4 gms. of dried copper phthalocyanine sulfinic acid having 2 sulfinic acid groups per molecule is prepared ac- 6 cording to Example 1 of British patent specification No. 960,643, published June 10, 1964, powdered, and blended with enough dry Na CO so that a 10% aqueous solution thereof would have pH 7.

The dry blend is dissolved to 800 ml. volume with Water, and 99 gms. 44% aqueous Na S is added thereto. The resulting solution is heated in a sealed vessel for 1 hour at 175 C., and the resulting slurry is cooled below 50 C., the solids product vcollected by filtration, washed with water at room temperature, and dried.

EXAMPLE 14 78.9 gms. of dried nickel phthalocyanine sulfinic acid having 2 sulfinic acid groups per molecule is prepared in the manner described in Example 1 of British patent specification No. 960,643, published June 10, 1964, except that 12.8 parts of nickel phthalocyanine tri-(3)-sulfonyl chloride mono-(3)-sulfonic acid is substituted for the 12.9 parts copper phthalocyanine tri-(3)-sulfonyl chloride mono-(3)-sulfonic acid used in the British patent.

The dried nickel phthalocyanine sulfinic acid is powdered, blended with enoughNa CO solids so that a 10% aqueous solution thereof would have pH 7, dissolved with Water to 800 ml. volume, and 142 gms. 25 aqueous Na S is added thereto. The resulting solution is heated in a sealed vessel 1 hour at 180 C., and the resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature, and dried.

EXAMPLE 15 79.2 gms. of the copper phthalocyanine sulfinic acid having an average of 1.5 sulfinic acid groups per copper phthalocyanine molecule is prepared according to Example 6 of British patent specification No. 960,643, published June 10, 1964.

The dried copper phthalocyanine sulfinic acid is powdered and blended with enough Na CO solids so that a 10% aqueous solution thereof would have pH 7. The blend is dissolved to 900 ml. volume with water, and 185.5 gms. Na S O -SH O is added thereto. The resulting solution is heated in a sealed vessel for 3 hours at C., and the resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature, and dried.

EXAMPLE 16 An aqueous solution of (S O zNa) CuPe ( S O a-Na) wherein CuPc is the radical of copper phthalocyanine, is prepared by adding 77.3 gms. copper phthalocyanine di- (3)-sulfonyl chloride to a stirring solution of 50.5 gms. sodium sulfite in 500 ml. Water maintained at 20-30 C. during the addition and also maintained at pH 99.5 by adding soda ash as required. The resulting solution is stirred 10 hours at room temperature. 75 gms. NaCl is added, and enough concentrated HCl to precipitate the sulfinate as a sulfinic acid. The sulfinic acid is collected by filtration, washed with 300 ml. 5% aqueous HCl, and collected as moist press cake.

The moist press cake is dissolved in Water with addition of enough NaOH to give pH 9 and a volume of 900 ml. 88 gms. 35% aqueous Na s is added thereto, and the solution is heated in a sealed vessel 1 hour at C. The resulting slurry is cooled below 50 C., the solids product collected by filtration, washed with water at room temperature and dried.

EXAMPLE 17 This example is the same as Example 16 above, except that 76.8 gms. nickel phthalocyanine di-(4)-sulfonyl chloride is substituted for the copper phthalocyanine di- (3)-sulfonyl chloride used in Example 16, and except that 7 124 gms. Na S O -5H O is substituted for the aqueous Na S used in Example 16.

EXAMPLE 18 This example is the same as Example 16 above, except that 71.2 grns. phthalocyanine di-(3)-su1fonyl chloride is substituted for the copper phthalocyanine di-(3)sulfonyl ch-loride used in Example 16; except that NHAgOH is substituted for the NaOH of Example 16; except that the pH is adjusted to 8 instead of 9; and that 104 gms.

(NH4)2S2O3 is substituted for the aqueous Na S used in Example 16.

EXAMPLE 19' This example is the same as Example 16 above, except that 125 gms. K S O 'H O is substituted for the aqueous Na S used in Example 16.

For purposes of economy, Na S O aqueous waste derived from production of sulfur dyes, such as sulfur black dye made from di-nitrophenol, may be employed directly .as the source of the Na S O used in the method of the present invention.

What is claimed is:

'1. A process for making vattable, sulfur containing dyestuif comprising the step of heating at 140180 C. and pH 7-10 in a sealed pressure vessel until the dyestutf precipitates an excess of a reagent selected from the group consisting of Na S O K S O (NH S O and sodium polysulfide with an aqueous solution of a sulfinate of the phthalocy-anine series selected from the group consisting of a sulfinate of phthalocyanine, a sulfinate of copper p'htha'locyanine and a sulfinate of nickel phthalocyanine, wherein said sulfinate of the phthalocyanine series has 24 substituents including an average of 13.4 pendant sodium sulfinate groups per phthalocyanine molecule as substituents for hydrogen in the phenylene nuclei of the phthalocyanine and in which any remaining substituents are pendant sodium thiolsulfonate or pendant sodium sulfonate groups.

2. A process as defined in claim 1, and in which said sulfinate has the formula (SOz-Na); Po

(SOzS- )y wherein Fe is the radical of phthalocyanine, copper phthal-ocyanine or nickel phthalocyanine, x is a number from 1.2-2.3, y is a number from 0.8-2.3, and x+y is a number from 24.

3. A method as defined in claim 1, and further characterized in that said sulfinate is SOz-Na)2.a

CuPe

2SNa)i.1 wherein Cu-Pc is the radical of copper phthalocyanine; and further characterized in that said reagent is sodium polysulfide.

References Cited UNITED STATES PATENTS 2,453,953 11/1948 Wood 260314.5

JOHN D. RANDOLPH, Primary Examiner.

W. A. MODANCE, Examiner.

H. I. MOATZ, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,378,568 April 16, 1968 Wi'lson J. Bryan, Jr., et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 61, "equilibrium" should read equipment Signed and sealed this 25th day of November 1969.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer 

